Applied Petrochemical Research (2018) 8:29–38

https://doi.org/10.1007/s13203-018-0195-8

ORIGINAL ARTICLE

Reaction kinetics of ethane partial oxidation to acetic acid

Sulaiman I. Al‑Mayman1   · Moustafa A. Soliman2 · Abdulrahman S. Al‑Awadi3 · Yousef S. Al‑Zeghayer3,4

Received: 6 February 2018 / Accepted: 13 February 2018 / Published online: 7 March 2018
© The Author(s) 2018. This article is an open access publication

Abstract
The partial oxidation of ethane to ethylene and acetic acid on supported MoVNbPd/TiO2 (P25 of Degussa) has been investi-
gated. Pd was added in a nano-metallic form. The catalyst composition was also different from similar studied catalysts. This
results in a better selectivity towards acetic acid formation. The reaction was carried out in a tubular reactor at temperature
range 225–275 °C, total pressure range 0–200 psig and oxygen percentage in the feed gas of 10–40%. The feed gas contains
ethane and oxygen. In this work, we develop a kinetic model for the reaction for the developed catalyst. In this model, we
assume that oxidation reactions take place on different sites; ethane oxidation takes place on one site, ethylene oxidation
on another site, and CO is oxidized to ­CO2 on a third site. The model exhibits good agreement with the experimental data.

Keywords  Ethane · Ethylene · Acetic acid · Partial oxidation · MoVNbPd catalyst

Introduction addition of Pd makes the catalyst more selective towards

Acetic acid is mainly produced industrially on large scale
from methanol carbonylation which accounts for 65% of
world capacity, but gives rise to many problems, such as
corrosion and waste disposal. Other processes include acet-
aldehyde oxidation and ethane partial oxidation. A plant
for partial oxidation of ethane to acetic acid is operated by
SABIC of Saudi Arabia since 2005. Vinegar which is about
4–6% diluted form of acetic acid is obtained by fermentation
of renewable carbon sources containing ethanol. Acetic acid
is primarily used in the production of vinyl acetate monomer
(VAM), acetic anhydride and as a solvent in the production
of terephthalic acid (TPA).
MoVNb catalysts were shown [1] to be able to effect the
partial oxidation of ethane to ethylene and acetic acid. The
* Sulaiman I. Al‑Mayman
smayman@kacst.edu.sa
1
King Abdul Aziz City for Science and Technology, P.O.
Box 6086, Riyadh 11442, Saudi Arabia
2
Department of Chemical Engineering, The British University
in Egypt, El‑Sherouk City, P.O. Box 43, Cairo 11837, Egypt
3
Department of Chemical Engineering, King Saud University,
P.O. Box 800, Riyadh 11421, Saudi Arabia
4
King Saud University, P.O. Box 800, Riyadh 11421,
Saudi Arabia
acetic acid formation.
The design of industrial reactors for partial oxidation of
ethane over MoVNbPd catalyst requires a reliable kinetic
model. In this paper we attempt to obtain kinetic expression
for ethane partial oxidation based on known mechanisms
that are usually used in partial oxidation reactions.
The following three mechanisms are usually used in par-
tial oxidation reactions;
1. Langmuir–Hinshelwood (LH) in which the adsorbed
oxygen and adsorbed ethane on the active sites of the
catalyst react in the adsorbed states,
2. Eley–Rideal (ER) in which one of the reactants is
adsorbed and react in the adsorbed state with the other
reactant in the gas phase.
3. Mars–Van Krevelen redox (MvK) in which the oxidized
catalyst react with ethane and thus is reduced and is
reoxidized with molecular oxygen.
In the pioneering work of Thorsteinson et al. Mo–V–Nb
catalysts [1], have been reported as active for the partial
oxidation of ethane to ethylene and acetic acid using oxy-
gen. In their work the kinetics for M
­ o16V8Nb2.29 was derived
assuming LH mechanism. Two schemes have been suggested
to explain the mechanism. In one scheme, ethoxy–hydroxyl
species are formed and these decompose to ethylene. In
the second scheme a hydroxy–alkoxy is formed and this

13
Vol.:(0123456789)

30
decomposes to ethylene and water. Bare metal sites M reacts
with water to form MOH which reacts with ethylene to give
an ethoxide ­MOC2H5. The ethoxide is oxidized to acetic
acid.
For acetic acid production, a pressure of about 300 psig
gives acetic acid selectivity about 20%, and ethylene selec-
tivity about 70%. In addition, the use of high pressure is
advantageous in reducing contact time for a specified ethane
conversion and thus reducing the catalytic reactor bed.
To avoid the formation of inflammable mixture, the feed
to the reactor contains low percentage of oxygen limiting
ethane conversion. This requires the recycle of unreacted
ethane.
The kinetics of Thoresteinson et al. has been used for
simulation of fixed bed reactor [2], and fluidized bed reac-
tor [3]. To avoid the formation of inflammable mixture, El-
Sherehy et al. [4] studied the use of distributed oxygen along
the reactor bed.
Karim et al. [5] showed that the addition of Pd to the
MoVNb catalyst greatly increases the selectivity to acetic
acid to about 80% and completely oxidizes CO to ­CO2.
Fakeeha et al. [6] obtained the kinetics for MoVPO cata-
lyst. A model based on Eley–Rideal and Mars and Van Krev-
elen redox mechanisms were found adequate.
The mechanism and kinetics of the reaction with a
­Mo1V0.25Nb0.12Pd0.0005Ox catalyst were studied by Linke
et al. [7, 8]. It has been shown that ethylene inhibits ethane
oxidation through depletion of lattice oxygen (O*). The con-
secutive oxidation of ethylene to acetic acid is itself cata-
lyzed by the palladium oxide in a heterogeneous analogue
of the Wacker process.
Their kinetic model contains some negative activation
energy which is physically wrong. They have indicated that
the C–H bond activation in ethane by the oxygen-saturated
catalyst surfaces is the rate limiting step [7]. Water is also
believed to increase acetic acid selectivity by promoting the
desorption of acetate species as acetic acid [7].
The kinetics of MoV type catalyst was re-investigated by
Rahman et al. [9] but the catalyst composition was not men-
tioned. Most probably it contains Nb and Pd. Rahman et al.
[9] developed a two-site Eley–Rideal-Redox (ERR) model
to predict the partial oxidation of ethane to ethylene and the
partial ethane oxidation to acetic acid over the catalyst. To be
used in acetic acid plant design, we need to know how much
CO is produced. However, their model assumes that the oxi-
dation of ethylene and acetic acid to CO is insignificant.
Also the oxidation of ethane to CO and ­CO2 is negligible.
Li and Iglesia [10, 11] found that precipitation of Mo,
V and Nb salts solution in the presence of colloidal T ­ iO2
(titania P25 from Degussa) led to a tenfold increase in
ethylene and acetic acid rates (per active oxide) with-
out significant changes in selectivity relative to unsup-
ported samples. The introduction of trace amounts of Pd
13
Applied Petrochemical Research (2018) 8:29–38
(0.0025–0.01 wt%) as a physical mixture of separate 0.3
(wt%) Pd/SiO2 led to the near complete depletion of eth-
ylene and to a significant increase in acetic acid synthesis
rate.
A suitable kinetic model for the catalytic oxidation of
ethane to acetic acid on MoVNb catalyst must be able to
explain the following key observations:
1. Rate of depletion of ethane is first order with respect to
ethane as noted by Thorsteinson et al. [1]. Burch and
Swarnakar [12] determined the rate of reaction to be
0.8–1.0 with respect to ethane depending on tempera-
ture.
2. Rate of depletion of ethane is a fraction close to zero
with respect to oxygen as noted by Thorsteinson et al.
[1]. Burch and Swarnakar [12] determined the rate of
reaction to be 0.07–0.5 with respect to oxygen.
3. High pressure favors the formation of acetic acid.
4. Temperature increase makes the reaction more selective
to ethylene with respect to acetic acid.
5. The strong acceleration of the rate of the ethylene oxida-
tion to acetic acid by the presence of water (Linke et al.
[7, 8]; Rahman et al. [9]). Water, whether formed as a
byproduct or added with C ­ 2H6–O2 reactants, increases
acetic acid selectivity by promoting the desorption of
adsorbed acetate species as acetic acid. Thus, the pro-
moting effect of water on acetic acid selectivity reflects
a specific increase in the rate at which ethane converts
to acetic acid via direct pathways. The absence of water
led to larger (ethylene/acetic acid) ratios in products and
to slightly higher ­COx selectivity.
6. Palladium catalyzes the oxidation of CO to C ­ O2. Ber-
lowitz et al. [13] have shown that for some range of
operating conditions the rate of CO oxidation is first
order in oxygen and negative first order in CO.
The catalyst used in our experiments has the composi-
0
tion ­Mo16V6.37Nb2.05OxPd0.0037 /TiO 2 (P25).The catalyst
loading on Titania is 30%. Pd was added. The method of
preparation, catalyst characterization and the effect of oper-
ating parameters for the partial oxidation reaction of ethane
such as temperature, space time and feed composition are
described in references [15, 16]. The experimental tubular
reactor used to carry out the experiments is also described
in these two references. This catalyst composition was opti-
mized for maximum acetic acid yield, and thus it is required
to develop a kinetic model for its use in the partial oxidation
reaction of ethane to acetic acid.
In the next section, the experiments carried out and the
results are presented. This is followed by the kinetic model
suggested. Parameter estimation results are then presented.
The results are then discussed and reaction mechanism is
suggested. Finally, conclusions are presented.
Applied Petrochemical Research (2018) 8:29–38 31
Experimental
The reaction system set up is described in Ref. [16].
Briefly 0.3 g of the catalyst diluted with silica particles
of the same size is placed in the reactor tube of overall
length 150 mm with inside diameter of made of 6.35 mm
stainless steel and surrounded by brass block. The block
is surrounded by mica band heater.
At the beginning of the experiments, we tested the
effect of reducing the catalyst particle size on ethane con-
version. No noticeable change happened. We concluded
that intraparticle mass transfer is negligibly small.
For the present kinetic study sixty-three experiments
were carried out for ethane oxidation. Temperatures varied
between 225 and 275 °C, pressures from atmospheric to
200 psig, total gas inlet flow-rate containing ethane and
oxygen from 10 to 40 ml/min, and ­O2% in the feed between
10 and 40. In all experiments, catalyst weight was 0.3 g.
Specifically, the following experiments were carried out:
1. At pressure 200 psig, and flow-rate 10 ml/min;
  (a) One experiment at 225 °C and 10% ­O2
  (b) Two experiments at 225, 240 °C and 20% ­O2
  (c) One experiment at 225 °C and 40% ­O2
2. At pressure 200 psig, and flow-rate 20 ml/min;
  (a) Two experiments at 225, 240 °C and 10% ­O2
  (b) Three experiments at 225, 240, 250 °C and 20%
­O2
  (c) Three experiments at 225, 250, 275 °C and 40%
­O2
3. At pressure 200 psig and flow-rate 40 ml/min
  (a) Two experiments at 225, 250 °C and 10% ­O2
  (b) Four experiments at 225, 250 °C and 20 and 40%
­O2
4. At pressure 100 psig and flow-rate 10 ml/min
  (a) One experiment at 225 °C and 10% ­O2
  (b) Two experiments at 225, 250 °C and 20% ­O2
  (c) Three experiments at 225, 250, 275 °C and 40%
­O2
5. At pressure 100 psig and flow-rate 20 ml/min,
  (a) One experiment at 225 °C and 10% ­O2
  (b) Two experiments at 225, 250 °C and 40% ­O2.
6. At pressure 100  psig and flow-rate 40  ml/min, nine
experiments at 225, 250, 275 °C and 10, 20 and 40% ­O2.
7. At pressure 0 psig, twenty-seven experiments at 225,
250, 275 °C and 10, 20 and 40% ­O2, flow-rates of 10, 20
and 40 ml/min.
The results are shown in Table 1.
Some observations can be made from testing results:
1. Acetic acid is not formed at atmospheric pressure.
2. Ethylene is the primary product at low temperature and
low pressure.
3. Ethylene selectivity decreases with the increase of tem-
perature.
4. Acetic acid is the primary product at high pressure and
low temperature.
5. In all experiments the selectivity of CO was very low.
6. The selectivity of ­CO2 increases with the increase of
temperature and the increase in ­O2% in the feed.
7. The pressure range for the experiments is very wide with
high selectivity to ethylene and ­CO2 at low pressure and
high selectivity to acetic acid at high pressure. It would
be a challenge to find a model that is suitable for wide
variation in the pressure.
Kinetic modeling of partial oxidation
of ethane
Here we attempt to obtain kinetic expression based on
known mechanisms that are usually used in partial oxi-
dation reactions. These are Langmuir–Hinshelwood (LH)
kinetics assuming reaction taking place between adsorbed
species, Eley–Rideal kinetics assuming reaction taking
place between adsorbed species and gaseous reactant, and
Mars–Van Krevelen redox mechanism in which the oxi-
dized catalyst react with ethane and thus is reduced and is
reoxidized with molecular oxygen.
For the reaction
1
A + O2 → B + H2 O, (1)
2
where A could be a hydrocarbon and B is the corresponding
dehydrogenated hydrocarbon.
Langmuir–Hinshelwood kinetics takes the form
kPm1 Pm2
Rate of oxidation reaction = [
A O2
]m3 .
1 + K1 PO2 + K2 PA + K3 PB + K4 Pw
(2)
While the redox kinetics take the form
kPA PO2
Rate of oxidation reaction = . (3)
PO2 + KPA
The reaction network is assumed in its most general form
of Fig. 1 (ri’s denote reaction rates of different species).
This assumes that acetic acid can be obtained from
ethane and ethylene and that all reactants and products
are oxidized to CO and ­CO2 and CO is converted to ­CO2.
We assume the conversion of ethane is X 1, the con-
version to CO is X2, ­CO2 is X3, and ­CH3COOH is X4. In
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32 Applied Petrochemical Research (2018) 8:29–38

Table 1  Results of kinetic study

Pressure Flow O2 Temp. °C O2 conv. % C2H6 conv. % Selectivity (%) Space time yield
psig ccm/min In feed % gm/kg h
Ethylene Acetic acid CO CO2 Acetic acid Ethylene

200 10 10 225 99.49 4.04 2.06 82.79 0.00 15.15 161.26 1.87
200 10 20 225 74.98 6.37 1.08 83.81 0.31 14.8 228.80 1.38
200 10 20 240 99.32 9.25 0.37 81.79 0.09 17.74 324.23 0.69
200 10 40 225 42.68 9.52 0.83 77.01 0.28 21.88 235.64 1.19
200 20 10 225 66.09 3.26 6.71 77.84 0.67 14.78 244.69 9.84
200 20 10 240 99.42 4.89 4.08 79.47 0.4 16.05 374.72 8.98
200 20 20 225 42.09 4.80 2.62 81.76 0.47 15.15 336.38 5.03
200 20 20 240 72.71 7.31 1.43 79.75 0.32 18.50 499.68 4.18
200 20 20 250 97.16 9.56 0.82 78.82 0.22 20.15 645.86 3.14
200 20 40 225 24.31 6.44 2.59 82.00 0.56 14.85 339.47 5.00
200 20 40 250 62.54 15.18 0.73 71.2 0.23 27.84 694.79 3.32
200 20 40 275 99.94 21.96 0.15 64.64 0.16 35.06 912.51 0.99
200 40 10 225 30.68 1.78 12.76 71.61 1.32 14.32 245.82 20.44
200 40 10 250 79.12 3.50 4.99 76.65 0.52 17.84 517.37 15.72
200 40 20 225 17.12 2.21 10.29 76.17 1.36 12.18 288.57 18.19
200 40 20 250 49.97 6.12 2.67 78.79 0.54 18.00 826.60 13.07
200 40 40 225 12.21 3.01 6.99 74.77 1.26 16.99 289.35 12.62
200 40 40 250 27.21 7.93 2.44 74.1 0.59 22.88 755.48 11.61
100 10 10 225 75.53 2.88 2.30 82.83 0.15 14.718 115.01 1.49
100 10 20 225 43.54 4.53 1.95 81.9 0.17 15.98 159.00 1.77
100 10 20 250 99.04 11.08 0.76 82.45 0.17 16.62 391.50 1.68
100 10 40 225 21.34 6.15 1.67 77.46 0.15 20.72 153.12 1.54
100 10 40 250 61.19 14.95 0.72 73.97 0.17 25.14 355.44 1.62
100 10 40 275 99.96 23.14 0.24 68.41 0.11 31.24 508.81 0.83
100 20 10 225 21.82 2.14 11.89 75.19 2.06 10.87 155.16 11.45
100 20 40 225 11.03 3.57 6.92 74.61 0.89 17.57 171.23 7.41
100 20 40 250 31.62 8.38 2.32 71.00 0.50 26.18 382.48 5.83
100 40 10 225 12.16 0.50 84.34 0.00 0.97 14.69 0.00 37.95
100 40 10 250 42.77 1.20 27.22 45.30 2.27 25.22 104.83 29.40
100 40 10 275 96.39 4.02 16.47 57.54 1.13 24.86 446.09 59.59
100 40 20 225 7.26 1.63 27.52 61.33 2.05 9.10 171.37 35.89
100 40 20 250 25.57 2.61 16.14 59.04 2.31 22.51 264.16 33.70
100 40 20 275 76.45 8.18 3.39 70.68 0.6 25.33 991.11 22.18
100 40 40 225 5.82 1.20 31.99 45.25 3.59 19.17 69.81 23.03
100 40 40 250 14.77 4.80 6.96 72.73 1.53 18.78 448.84 20.05
100 40 40 275 43.92 11.96 1.77 67.05 0.70 30.48 1031.01 12.70
0 10 10 225 15.25 0.98 100.00 0.00 0.00 0.00 0.00 22.05
0 10 10 250 41.76 1.98 86.15 0.00 2.54 11.31 0.00 38.38
0 10 10 275 90.01 3.56 58.51 0.00 6.89 34.60 0.00 46.87
0 10 20 225 8.35 1.01 100.00 0.00 0.00 0.00 0.00 20.20
0 10 20 250 21.85 2.02 80.07 0.00 1.34 18.59 0.00 32.35
0 10 20 275 58.42 3.75 49.13 0.00 7.11 43.76 0.00 36.85
0 10 40 225 3.12 1.30 91.42 0.00 0.00 8.58 0.00 17.83
0 10 40 250 11.75 2.50 74.55 0.00 2.66 22.78 0.00 27.96
0 10 40 275 35.46 4.80 37.33 0.00 9.07 53.60 0.00 26.88
0 20 10 225 6.83 0.52 100 0.00 0.00 0.00 0.00 23.40
0 20 10 250 16.61 1.13 90.22 0.00 0.00 9.79 0.00 45.88

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Applied Petrochemical Research (2018) 8:29–38 33

Table 1  (continued)
Pressure Flow O2 Temp. °C O2 conv. % C2H6 conv. % Selectivity (%) Space time yield
psig ccm/min In feed % gm/kg h
Ethylene Acetic acid CO CO2 Acetic acid Ethylene

0 20 10 275 48.95 2.11 74.38 0.00 3.29 22.33 0.00 70.62

0 20 20 225 3.82 0.57 100 0.00 0.00 0.00 0.00 22.80
0 20 20 250 7.20 1.25 91.10 0.00 0.00 8.90 0.00 45.55
0 20 20 275 29.73 2.65 63.67 0.00 9.03 27.31 0.00 67.49
0 20 40 225 1.88 0.73 100 0.00 0.00 0.00 0.00 21.90
0 20 40 250 4.59 1.49 85.21 0.00 0.00 14.79 0.00 38.09
0 20 40 275 15.84 3.27 55.29 0.00 10.92 33.79 0.00 54.24
0 40 10 225 4.96 0.38 100 0.00 0.00 0.00 0.00 34.20
0 40 10 250 11.12 0.75 100 0.00 0.00 0.00 0.00 67.50
0 40 10 275 29.77 1.51 85.81 0.00 2.77 11.42 0.00 116.62
0 40 20 225 3.24 0.43 100 0.00 0.00 0.00 0.00 34.40
0 40 20 250 6.66 0.82 100 0.00 0.00 0.00 0.00 65.60
0 40 20 275 17.43 1.76 80.34 0.00 3.01 16.66 0.00 113.12
0 40 40 225 2.86 0.49 100 0.00 0.00 0.00 0.00 29.40
0 40 40 250 3.48 1.12 89.98 0.00 0.00 10.02 0.00 60.47
0 40 40 275 8.14 2.17 70.64 0.00 2.66 26.70 0.00 91.97

dX4
= rCH3 COOH (8)
d𝜏
With the initial conditions at
W
𝜏=
FC2 H6
= 0, X1 = X2 = X3 = X4 = 0, (9)

where W = catalyst weight FC2H6 = volumetric flow-rate of

ethane in the feed.
The rate of depletion of ethane (rC2 H6 ) is given by
1 1
rC2 H6 = r1 + r2 + r3 + r4 , (10)
Fig. 1  Proposed scheme for ethane partial oxidation 2 2
where r1 is the rate of oxidation of ethane to ethylene; r2 is
the rate of oxidation of ethane to acetic acid; r3 is the rate
addition, we assume that the reactor operates in the inte- of formation of CO by ethane oxidation and r4 is the rate of
gral mode. Thus, we have formation of ­CO2 by ethane oxidation.
W The rate of formation of CO (rCO ) is given by
𝜏=
FC2 H6 (4)
rCO = r3 + r5 + r8 − r10 , (11)
where r5 is the rate of formation of CO from ethylene oxida-
dX1
= rC2 H6 (5) tion, r8 is the rate of formation of CO from acetic acid oxida-
d𝜏 tion, and r10 is the rate of oxidation of CO to ­CO2.
The rate of formation of ­CO2 (rCO2 ) is given by
dX2
= rCO (6) rCO2 = r4 + r6 + r9 + r10 , (12)
d𝜏
where r6 is the rate of formation of C
­ O2 from ethylene oxida-
dX3 tion, and r9 is the rate of formation of ­CO2 from acetic acid
= rCO2 (7) oxidation, and r10 is the rate of oxidation of CO to ­CO2.
d𝜏
The rate of formation of ­CH3COOH (rCH3OOH) is given by

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34 Applied Petrochemical Research (2018) 8:29–38

1 1 mol K. The dependence of the adsorption constants (K’s) on

rCH3 OOH = r2 + r7 − r8 − r9 ,
2 2 (13) temperature was insignificant.
The calculated conversions are obtained by integrating
where r7 is the rate of formation of acetic acid from ethylene.
equations subject to the initial condition. The pressures of the
The expressions for r1–r10 are given by
different components in terms of conversions are obtained as
k1 × PC2 H6 × PO2 follows.
r1 = (14) Let X1 be the conversion of ethane, X2 number of moles of
PO2 + K1 × PC2 H6
CO produced per mole of ethane, X3 number of moles of C ­ O2
produced per mole of ethane X4 number of mole of ­CH3COOH
k2 × P2C H × P2O produced per mole of ethane.,
r2 = 2 6 2
(15) Y1 moles of O­ 2 per mole of ethane and nt total number of
(PO2 + K1 × PC2 H6 )2 moles of products per mole of ethane. Thus

C2 H6 + 21 O2 → C2 H4 + H2 O
k3 × PC2 H6 × PO2
r3 = (16) −X1 − 21 X1 X1 X1
PO2 + K1 × PC2 H6

C2 H4 + O2 → CH3 COOH
k4 × PC2 H6 × PO2 −X4 − X4 X4
r4 = (17)
PO2 + K1 × PC2 H6
C2 H4 + 3O2 → 2CO2 + 2H2 O
− 12 X3 − 23 X3 X3 X3
k5 × PC2 H4 × PO2
r5 = (18)
PO2 + K2 × PC2 H4 Moles of ethane = 1−X1 (25)

1 3
Moles of oxygen = Y1 − X1 −X2 − X3 −X4 (26)
k6 × PC2 H4 × PO2 2 2
r6 = (19)
PO2 + K2 × PC2 H4
1 1
Moles of ethylene = X1 − X2 − X3 − X4 (27)
2 2
k7 × P2C H × PO2 × PH2 O
r7 = 2 4
(20) Moles of CH3 COOH = X4 (28)
PO2 + K3 × PC2 H4
Moles of CO = X2 (29)
k8 × PCH3 COOH × PO2 Moles of CO2 = X3 (30)
r8 = (21)
PO2 + K3 × PC2 H4
Moles of H2 O = X1 + X2 + X3 (31)

1 1
k9 × PCH3 COOH × PO2 Total moles (nt) = 1 + Y1 + X1 + X2 − X4 . (32)
r9 = (22) 2 2
PO2 + K3 × PC2 H4
Thus, the partial pressures of the different compounds are
as follows:
k10 × PCO × PO2
r10 = , (23) (1 − X1 )
(PCO + K4 PO2 )2 PC2 H6 = Pt (33)
nt

with the k’s are defined as ( )

Y1 − 21 X1 − X2 − 32 X3 − X4
−Ei ( 1 1
)
PO2 = Pt (34)
ki = ki,o × exp − , (24) nt
R T 548.15
where: all pressures are in atmosphere, the rates are in ­Ncm3/ ( )
min g, ki’s units can be deduced. Ki’s are dimensionless, Ei X1 − 12 X2 − 21 X3 − X4
PC2 H4 = Pt (35)
is activation energy in cal/mol, T is in K and R = 1.98 cal/ nt

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Applied Petrochemical Research (2018) 8:29–38 35

X4 and 95% confidence regions of the parameter estimation and

PCH3 COOH = P (36) some others.
nt t
If the F value is small, the fit of the model is poor. At
X2 fixed number of parameters and experiments the higher is
PCO = P (37) the F value the better is the fit. If a parameter is found to
nt t
have very small t value, it means that it does not have a sig-
X3 nificant effect in determining the reaction rates and should
PCO2 = P (38) be eliminated from the rate equations.
nt t

(X1 + X2 + X3 )
PH2 O = Pt ,
nt
where Pt = total pressure
Parameter estimation was done by the minimization of
weighted residual squares of the conversions. The resulting
non-linear equations are solved by Marquardt method. The
method used is described in details by Hosten et al. [14].
The computer package for carrying out estimation calcu-
lations provides statistical data. They are F value for judg-
ing goodness of fit. t values for significance of parameters
(39) Parameter estimation results
Preliminary screening led us to conclude that the rate of
oxidation of ethane to acetic acid and CO is negligibly small,
i.e., r2 = 0 and r3 = 0 . In addition, the rate of oxidation of
ethylene to CO and C ­ O2 is negligibly small, i.e., r5 = 0
and r6 = 0 . We obtain the following parameter estimates
(Table 2).

Table 2  Parameter estimates; Parameter estimate 95% Confidence t value

F = 342.6, residual sum of
squares = 0.024 Lower limit Upper limit

k1,0 1.43537 1.20362 1.66711 1.23874D + 01

k2,0 0 n.a. n.a. n.a.
k3,0 0 n.a. n.a. n.a.
k4,0 1.53309 1.24128 1.82491 1.05074D + 01
k5,0 0 n.a. n.a. n.a.
k6,0 0 n.a. n.a. n.a.
k7,0 1.77704D + 04 − 9.17674D + 03 4.47176D + 04 1.31891
k8,0 4.73845D − 01 2.41522D − 01 7.06168D − 01 4.07919
k9,0 2.09258D − 01 5.01612D − 02 3.68354D − 01 2.63057
k10,0 2.96836D − 04 2.32607D − 04 3.61064D − 04 9.24314
E1 1.30413D + 04 1.11920D + 04 1.48907D + 04 1.41036D + 01
E2 n.a. n.a. n.a. n.a.
E3 n.a. n.a. n.a. n.a.
E4 2.69857D + 04 2.38892D + 04 3.00823D + 04 1.74294D + 01
E5 n.a. n.a. n.a. n.a.
E6 n.a. n.a. n.a. n.a.
E7 1.26698D + 04 − 8.13832D + 03 3.34780D + 04 1.21778
E8 = E9 1.91947D + 03 − 6.76769D + 03 1.06066D + 04 4.41910D − 01
E10 2.13033D + 04 9.87802D + 03 3.27286D + 04 3.72915
K1 3.01309D − 01 1.96877D − 01 4.05741D − 01 5.77045
K2 n.a. n.a. n.a. n.a.
K3 5.83161D − 01 − 1.20871D + 00 2.37504D + 00 6.50896D − 01
K4 1.00648D − 04 7.93151D − 05 1.21982D − 04 9.43570

The values of the rate of reactions considered in this work are based on the units of normal ­cm3/min g
They must be multiplied by 0.00268 to transform them to the more usual units of mol/h g catalyst
n.a. not applicable

13

36 Applied Petrochemical Research (2018) 8:29–38

Discussion from the second route is not significant. The first route involv-
ing water needs modification. Let Y be a catalytic center for
We were not able to fit our experimental results with the ethylene oxidation to acetic acid. Consider the following
model of Rahman et al. [9]. Thus, the model needs modifi- scheme;
cations for our case since we are using a different catalyst. 2Y + 2O2 ⇄ 2YO2
Parameter estimation results indicate that the main reactions
taking place are the oxidation of ethane to ethylene and C ­ O2 C2 H4 + Y ⇄ C2 H4 Y
and the oxidation of ethylene to acetic acid. Some of acetic
acid is also oxidized to CO and C ­ O2. CO is oxidized to C ­ O2. 2C2 H4 + YO2 ⇄ (CH3 CH)2 OYO
The final reaction network takes the form of Fig. 2.
(CH3 CH)2 OYO + H2 O ⇄ (CH3 CH)2 OY(OH)2
The results indicate that oxidation reactions take place
on different sites. Ethane oxidation takes place on one site. (CH3 CH)2 OY(OH)2 → (CH3 CHO)2 Y + H2 O (RDS)
Ethylene oxidation in presence of water to acetic acid takes
place on another site. CO is oxidized to ­CO2 on a third site. (CH3 CHO)2 Y + YO2 → 2CH3 COOH + 2Y (fast).
The estimation results indicate that a redox mechanism This leads to the following rate equation
is more suitable to explain the reactions taking place for the
oxidation of ethane to ethylene. Equation (14) for ethane k7 × P2C × PO2 × PH2 O
2 H4
oxidation to ethylene takes the familiar form of redox kinet- r7 = k
1 + k(PO2 + K3 × PC2 H4 + negligibe adsorption terms … .)
.
ics. The parameters associated with the oxidation of ethane
to ethylene are determined with large t values giving high For large k this equation simplifies to Eq. (20).
confidence in their values. For the oxidation of ethane to For the oxidation of acetic acid to CO and C­ O2, we suggest
ethylene, our results agree with Linke et al. [7]. For the oxi- the following scheme
dation of ethylene to acetic acid our results also agree with
3 3 3
that of Linke et al. [7] that acetic acid is related to the forma- Y + O2 ⇄ YO2
2 2 2
tion of a hydroxyl group from water on the active site. There
are some controversy of whether ethane or ethylene oxidizes
1 1 1
to CO and C ­ O2. Burch and Swanakar [12] suggested that Y + O2 ⇄ YO
CO and C ­ O2.are formed to a large extent from ethane. On 2 4 2
the contrary Thorsteinson et al. [1] suggested that ethylene
CH3 COOH + YO2 → CH3 COOHYO2 (RDS)
oxidizes into CO and ­CO2. Our results suggest that ­CO2 is
mainly obtained from ethane and acetic acid whereas CO is 1 1
obtained from acetic acid. This CO is then oxidized to C ­ O2 2
CH3 COOHYO2 + YO2 → CO2 + H2 O + Y (fast)
2
on sites containing Pd. For reactions involving ethylene, ace-
tic acid and CO a LH kinetic model is suggested. 1 1
For the oxidation of ethylene to acetic acid, Rahman et al. 2
CH3 COOHYO2 + YO → CO + H2 O + Y (fast),
2
[9] suggested two routes one involves water and the second
does not involve water. We found that acetic acid formation which leads to the following rate equations
k8 × PCH3 COOH × PO2
r8 = k ,
1 + k(PO2 + K3 × PC2 H4 + negligibe adsorption terms … .)

k9 × PCH3 COOH × PO2

r9 = k .
1 + k(PO2 + K3 × PC2 H4 + negligibe adsorption terms … .)

For large k, these two equations can be approximated by

Eqs. (21) and (22).
For the oxidation of CO to C ­ O2 this occurs through
adsorbed oxygen and adsorbed CO on a site denoted by Z
such that
1
Z + O2 ⇄ ZO
2

Fig. 2  Modified scheme for ethane partial oxidation 2ZO ⇄ ZO2 + Z

13
Applied Petrochemical Research (2018) 8:29–38 37

1
ZO + O2 ⇄ ZO2
2

CO + Z ⇄ COZ
COZ + ZO2 → CO2 Z + ZO (RDS)

CO2 Z → CO2 + Z (fast)

k10 × PCO × PO2

r10 = k × k ( )2 .
1 + k(PCO + K4 PO2 )

For large k this equation can be approximated by Eq. (23).

The order of magnitude of the activation energies is
similar to the values reported in the literature [1, 8, 9].
Large activation energy means that the reaction is favored
at high temperature. Thus, it is noticed from the values
of activation energy and from experimental results that
higher temperature favors the formation of C ­ O2 from oxi-
dation of ethane. Fig. 4  Observed and calculated yield of C
­ O2 for partial oxidation of
Figures 3, 4 and 5 show the goodness of fit between ethane
the observed ethane conversion, C ­ O2 yield and acetic acid
yield and that calculated from the kinetic model. Reason-
able fit is obtained for high conversion which would be of Conclusion
practical importance. For low conversion, the fit is slightly
distorted possibly because inaccuracy in the experimental Our kinetic model has a phenomenological and statistical
results. significance. We assumed a general network, but found
through model development and parameter estimation of
model parameters that the significant reactions are ethane

Fig. 3  Observed and calculated conversion for ethane partial oxida- Fig. 5  Observed and calculated values of acetic acid yield for partial
tion oxidation of ethane

13

38
oxidation to ethylene and ­CO2, ethylene to acetic acid, CO
and ­CO2, and CO to ­CO2. The analysis showed that ethane
oxidation to acetic acid and CO is not significant. The reac-
tion takes place on three sites, one for ethane oxidation to
ethylene, the second for ethylene oxidation to acetic acid,
CO and ­CO2, and the third for the oxidation of CO to ­CO2
In spite of reasonable acetic acid selectivity, there is still
scope for catalyst improvement because of the high C ­ O2
selectivity.
Future work can be directed towards deep understanding
of all steps, such as ethylene oxidation, acetic acid oxidation,
CO oxidation with these experiments carried out in the pres-
ence and absence of water vapor. The species which lead to
the partial oxidation products should be identified.
Acknowledgements  The authors acknowledge the financial sup-
port provided by King Abdul Aziz City for Science and Technology
(KACST) for this research under Grant number AR-29-256.
Open Access  This article is distributed under the terms of the Crea-
tive Commons Attribution 4.0 International License (http://creat​iveco​
mmons​.org/licen​ses/by/4.0/), which permits unrestricted use, distribu-
tion, and reproduction in any medium, provided you give appropriate
credit to the original author(s) and the source, provide a link to the
Creative Commons license, and indicate if changes were made.
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